(S)-(+)-2-(methoxymethyl)-1-(1-phenylpropylideneamino)pyrrolidine | 107538-61-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S)-(+)-2-(methoxymethyl)-1-(1-phenylpropylideneamino)pyrrolidine
• 英文别名: (+)-(S)-2-methoxymethyl-1-(1-phenylpropylideneamino)-pyrrolidine；propiophenone (S)-1-amino-2-methoxymethylpyrrolidine hydrazone
• CAS: 107538-61-4
• 化学式: C₁₅H₂₂N₂O
• 分子量: 246.352
• InChiKey: NDVWTARQDHAMKJ-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.91
• 重原子数：
  18.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  24.83
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (S)-(+)-2-(methoxymethyl)-1-(1-phenylpropylideneamino)pyrrolidine 在 臭氧 、 lithium diisopropyl amide 作用下， 以 二氯甲烷 为溶剂， 生成 ((2S,3S)-2-Ethyl-3-methyl-4-oxo-4-phenyl-butyl)-phosphonic acid diethyl ester
  参考文献：
  名称：

  Diastereo- and enantioselective synthesis of 2,3- and 1,2-disubstituted 4-oxophosphonates via asymmetric Michael addition

  摘要：

  Asymmetric Michael addition of lithiated SAMP hydrazones (S)-2 to a variety of alkenylphosphonates (E)-3 followed by oxidative cleavage of the 1,4-adducts 4 afforded 2,3-disubstituted 4-oxophosphonates 5 with good to very good yields (58-80%), low to moderate diastereomeric (de = 6-74%) and excellent enantiomeric excesses (ee = >93%). Pure anti-diastereomers (ee = >93%) of 5 were obtained by separation of the stereoisomers by HPLC. In addition, the lithiated SAMP hydrazone (S)-2a was added to alkenylphosphonates (E)-3, and the lithio phosphonate anions were trapped with alkyl halides or sulfates, yielding 1,2-disubstituted 4-oxophosphonates 8 with moderate to good yields (38-69%), low to good diastereomeric (de = 10-77%) and high enantiomeric excesses (ee = >90%) after oxidative cleavage. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00814-4
• 作为产物：
  描述：

  (2S)-2-(甲氧基甲基)-N-(3-苯基亚丙基)-1-吡咯烷胺 在 lithium aluminium tetrahydride 、 臭氧 、 lithium diisopropyl amide 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 (S)-(+)-2-(methoxymethyl)-1-(1-phenylpropylideneamino)pyrrolidine
  参考文献：
  名称：

  Asymmetric Michael additions via SAMP-/RAMP-hydrazones anti-diastereo- and enantioselective synthesis of 3,4-disubstituted 5-oxo-alkanoates

  摘要：

  DOI：

  10.1016/s0040-4039(00)84830-3

文献信息

• Enantioselective synthesis of protected α-hydroxy aldehydes and ketones via hydroxylation of metalated chiral hydrazones
  作者：Dieter Enders、Vidya Bhushan

  DOI：10.1016/s0040-4039(00)87901-0

  日期：1988.1

  α-Benzyloxy aldehydes and α-acetoxy ketones 4 of high enantiomeric purity are prepared in good overall yields via oxaziridine mediated hydroxylation of chiral hydrazone azaenolates. As auxiliaries novel proline derived hydrazine reagents 5 are used.

  高的对映体纯度的α-苄氧基醛和α-乙酰氧基酮4通过恶唑烷介导的手性氮杂酸酯的羟基化反应以良好的总收率制备。作为助剂，使用了新的脯氨酸衍生的肼试剂5。
• Asymmetric syntheses via metalated chiral hydrazones
  作者：D. Enders、H. Eichenauer、U. Baus、H. Schubert、K.A.M. Kremer

  DOI：10.1016/s0040-4020(01)82420-0

  日期：1984.1

  ee up to virtually complete asymmetric induction (99.5% ee). The acyclic ketones are transformed to their corresponding “SAMP-hydrazones” (S)-2 by reaction with the enantiomerically pure hydrazine (S)-l-amino-2-methoxymethyl-pyrrolidine [SAMP, (S)-1], readily available from (S)-proline. Metalation to form chiral azaenolates (S)-3 of EccZcn-configuration and then alkylation to product hydrazones 4 followed

  描述了一种通用方法，该方法可使无环酮的整体对映选择性α-烷基化具有良好的总收率（44–86％，4步），对映选择性通常从> 94％ee到几乎完全不对称诱导（99.5％ee） ）。通过与对映体纯的肼（S）-1-氨基-2-甲氧基甲基-吡咯烷[ SAMP，（S）-1 ]反应，将无环酮转化为相应的“ SAMP- azo”（S）-2来自（S）-脯氨酸。金属化形成E cc Z cn的手性氮杂酸酯（S）-3-构型，然后烷基化为产物4，然后在两相系统中通过甲硫氨酸9的酸性水解或臭氧分解裂解，可生成α-取代，对映体富集的无环酮5。在特殊情况下，当苯基直接连接到新生成的手性中心（5n，o，p）时，仅观察到低对映体过量。总结了17个示例，包括天然产物合成中的第一个应用（参见5abe和h）
• Diastereo- and Enantioselective Synthesis of<i>syn</i>-2,3-Disubstituted 1,4-Diketones<i>via</i>Oxidative Coupling of Metalated Hydrazones
  作者：Dieter Enders、Peter Müller、Daniela Klein

  DOI：10.1055/s-1998-1562

  日期：1998.1

  An efficient diastereo- and enantioselective synthesis of syn-2,3-disubstituted 1,4-diketones 4 is described. Key step of the procedure is the oxidative coupling of the metalated SAMP/RAMP-hydrazones 2 with iodine, followed by oxidative cleavage of the dimerized bishydrazones 3 with ozone and subsequent separation of the minor meso-isomer by chromatography. The d,l-isomers of the title 1,4-diketones 4 are obtained in good overall yields (20-64%) and high diastereo- and enantiomeric excesses (de ≥ 98%, ee = 80- ≥ 95%).

  本文描述了syn-2,3-二取代-1,4-二酮4的高效对映选择性和非对映选择性合成方法。该过程的关键步骤是金属化的SAMP/RAMP脒2与碘的氧化耦合反应，随后用臭氧氧化断开二聚的双脒3，并通过色谱法分离出次要的内消旋异构体。标题1,4-二酮4的d,l异构体以良好的总收率（20-64%）和高度的非对映选择性及对映体过量（de ≥ 98%，ee = 80- ≥ 95%）获得。
• Enantioselective synthesis of α-sulfenylated ketones and aldehydes via α-thiolation of metalated SAMP/RAMP hydrazones
  作者：Dieter Enders、Thomas Schäfer、Wolfgang Mies

  DOI：10.1016/s0040-4020(98)00481-5

  日期：1998.8

  Asymmetric α-sulfenylation of lithiated SAMP/RAMP hydrazones (S)-2 with disulfides afforded α-thiolated hydrazones (S,R)-3 in good yields (48–87%) and high diastereomeric excesses (91–96%). Subsequent oxidative cleavage or acidic hydrolysis of the hydrazones furnished α-thiolated ketones (R)-4a-d with high enantiomeric excesses (87–>96%). α-Sulfenylated aldehydes (R)-8a-d were prepared by a similar reaction

  锂化的SAMP / RAMP hydr（S）-2与二硫化物的不对称α-亚磺酰化提供了高收率（48–87％）和高非对映异构体过量（91–96％）的α-硫醇化（S，R）-3 。hydr的随后氧化裂解或酸水解提供了高对映体过量（87-> 96％）的α-硫醇化酮（R）-4a-d 。通过类似的反应顺序，以45–93％ee制备α-亚磺酰醛（R）-8a-d 。
• Enders, Dieter; Lohray, Braj Bhushan, Angewandte Chemie, 1987, vol. 99, # 4, p. 359 - 360
  作者：Enders, Dieter、Lohray, Braj Bhushan

  DOI：——

  日期：——